CN109659528B - Potassium ion battery negative electrode active material, potassium ion battery negative electrode, potassium ion battery and application thereof - Google Patents

Potassium ion battery negative electrode active material, potassium ion battery negative electrode, potassium ion battery and application thereof Download PDF

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CN109659528B
CN109659528B CN201811539680.9A CN201811539680A CN109659528B CN 109659528 B CN109659528 B CN 109659528B CN 201811539680 A CN201811539680 A CN 201811539680A CN 109659528 B CN109659528 B CN 109659528B
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potassium
ion battery
negative electrode
potassium ion
carbon
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CN109659528A (en
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唐永炳
李娜
张帆
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a potassium ion battery negative electrode active material, a potassium ion battery negative electrode, a potassium ion battery and application thereof, and belongs to the technical field of potassium ion batteries. The invention provides a potassium ion battery cathode active material, which comprises a niobium pentoxide composite material; wherein the niobium pentoxide composite material comprises a niobium pentoxide composite material containing dopant ions and/or a coating layer. The niobium pentoxide composite material has an excellent potassium ion transmission channel, can realize the rapid intercalation and de-intercalation of potassium ions, has a stable crystal structure, adopts the reaction mechanism of intercalation and pseudocapacitance, has long cycle life, high specific capacity and low cost of the prepared potassium ion battery, can solve the problem of price rise caused by insufficient lithium resources, and avoids the problems of expansion and pulverization of an alloy type cathode of the potassium ion battery, slow dynamics of an intercalation type carbon material and the like. The energy-saving device can be widely applied to electric tools, electronic equipment, electric vehicles or energy storage equipment.

Description

Potassium ion battery negative electrode active material, potassium ion battery negative electrode, potassium ion battery and application thereof
Technical Field
The invention belongs to the technical field of potassium ion batteries, and particularly relates to a potassium ion battery negative electrode active material, a potassium ion battery negative electrode, a potassium ion battery and application thereof.
Background
In recent years, people have increasingly large demand for electric automobiles and portable electronic equipment, limited lithium resources are consumed more and more quickly, and novel energy storage systems capable of replacing lithium ion batteries are receiving more and more attention. Rich potassium resource, uniform distribution, low cost and K/K+The standard electrode potential is-2.94V, is closest to the standard electrode potential of lithium ions, has higher energy density, and can replace lithium to be used for batteries.
However, the radius of potassium ions is larger than that of lithium ions and sodium ions, so that the potassium ions cannot be reversibly intercalated/deintercalated in most negative electrode materials of lithium ion batteries, and cannot be applied, or the problem of slow kinetics exists, so that the rate performance and cycle performance of the battery are far inferior to those of the lithium ion batteries. Therefore, the potassium ion battery has more stringent requirements on the negative electrode material than the lithium ion battery or the sodium ion battery. At present, the reported negative electrode materials of the potassium ion battery are less and mainlyIt includes potassium plate, alloy type Sn and Bi cathode, and insertion layer type carbon material. The potassium metal is very active, and although the capacity is high by using a potassium sheet as a negative electrode, potential safety hazards are easy to generate; the alloy type metal Sn and Bi negative electrodes have higher specific capacity, but the radius of potassium ions is larger, the expansion coefficient of the metal is larger in the charging and discharging process, and the electrodes are easy to pulverize to cause poor cycle performance; potassium ions can intercalate a layered carbon material such as graphite at low pressure, but K+In graphite, the kinetics is slow, the diffusion coefficient is small, and the rate performance is poor.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a potassium ion battery negative active material, which comprises a niobium pentoxide composite material, wherein the niobium pentoxide composite material has a stable structure and can rapidly store K+The above problems are overcome or at least partially solved.
The second purpose of the invention is to provide a potassium ion battery negative electrode material, which comprises the potassium ion battery negative electrode active material, a conductive agent and a binder.
The third purpose of the invention is to provide a potassium ion battery negative electrode, which comprises the potassium ion battery negative electrode active material; the niobium pentoxide composite material has an excellent potassium ion transmission channel, can realize the rapid embedding and de-embedding of potassium ions, has a stable crystal structure, and does not generate phase change in the process of embedding and de-embedding of potassium ions.
The fourth purpose of the invention is to provide a preparation method of the potassium ion battery negative electrode.
A fifth object of the present invention is to provide a potassium ion battery. The potassium ion battery comprising the potassium ion battery cathode has the characteristics of long cycle life, high specific capacity and low cost.
A sixth object of the present invention is an application of the above potassium-ion battery to an electric tool, an electronic device, an electric vehicle, or an energy storage device.
According to a first aspect of the present invention, there is provided a potassium ion battery negative active material comprising a niobium pentoxide composite material;
wherein the niobium pentoxide composite material comprises a niobium pentoxide composite material containing dopant ions and/or a cladding layer.
Preferably, the dopant ions comprise at least one of K, Na, Li, Mg, Zn, Ca, N, S or P, preferably K;
preferably, the mass ratio of the doping ions to the niobium element is 1: 3-1: 7, preferably 1: 5;
preferably, the crystalline form of niobium pentoxide comprises at least one of an orthorhombic phase, a hexagonal phase and a monoclinic phase, preferably an orthorhombic phase.
The material of the coating layer comprises at least one of a carbon material and a metal oxide;
preferably, the carbon material comprises elemental carbon and/or a carbon-containing compound;
preferably, the carbon simple substance comprises at least one of graphite, expanded graphite, graphene, mesophase carbon microsphere graphite, acetylene black, glassy carbon, carbon-carbon composite material, activated carbon, hard carbon, carbon black, carbon nanotube, carbon nanofiber or mesoporous carbon;
preferably, the carbon-containing compound comprises at least one of citric acid, glucose, sucrose, starch, polyethylene oxide, polyethylene glycol, glycerol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl propyl cellulose, polyvinyl alcohol, polypropylene, phenolic resin, or epoxy resin;
preferably, the metal oxide comprises at least one of titanium dioxide, manganese dioxide and ferric oxide;
preferably, the material of the cladding layer comprises graphene;
preferably, the mass fraction of the material of the coating layer is 5 wt% to 20 wt%, preferably 10 wt%.
Preferably, the niobium pentoxide composite material is a niobium pentoxide composite material containing a coating layer, and preferably the niobium pentoxide composite material containing a carbon material as the coating layer. According to a second aspect of the present invention, there is provided a potassium ion battery negative electrode material comprising the above potassium ion battery negative electrode active material, a conductive agent and a binder.
According to a third aspect of the present invention, there is provided a potassium-ion battery anode comprising the above potassium-ion battery anode active material.
According to a fourth aspect of the present invention, there is provided a method for preparing the above potassium ion battery negative electrode, comprising the steps of:
dissolving a potassium ion battery negative electrode active material, a conductive agent and a binder in a solvent to prepare slurry, and then coating the slurry on the surface of a negative electrode current collector to obtain the potassium ion battery negative electrode.
According to a fifth aspect of the present invention, there is provided a potassium ion battery comprising the above potassium ion battery negative electrode or the potassium ion battery negative electrode prepared by the above preparation method, a positive electrode, a separator, and an electrolyte.
Preferably, the positive electrode comprises a layered metal oxide, a polyanion compound, or a prussian blue analog; preferably K0.67Fe0.5Mn0.5O2、FePO4、K0.5MnO2Or K2Fe2(CN)6Further preferably K0.67Fe0.5Mn0.5O2；
Preferably, the separator comprises a porous polymer film, an inorganic porous film or an organic-inorganic composite separator, preferably a porous ceramic film, a porous polypropylene film, a porous polyethylene film, a porous composite polymer film or glass fibers, and further preferably glass fibers;
preferably, the electrolyte comprises a potassium salt and a non-aqueous solvent;
preferably, the concentration of the potassium salt in the electrolyte is 0.1-8mol/L, preferably 0.5-1 mol/L;
preferably, the potassium salt includes at least one of potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalato borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methylsulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonylimide, or potassium trifluoromethanesulfonate, preferably potassium hexafluorophosphate.
Preferably, the non-aqueous solvent comprises ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N-dimethyl acetamide, fluoroethylene carbonate, ethyl propionate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, at least one of 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite or crown ether, preferably a mixed solvent of ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate;
preferably, in the mixed solvent of ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the volume ratio of the ethylene carbonate, the propylene carbonate, the dimethyl carbonate and the ethyl methyl carbonate is 2:2:3: 3.
According to a sixth aspect of the present invention, there is provided the use of the above potassium ion battery in an electric tool, an electronic device, an electric vehicle, or an energy storage device.
The invention provides a potassium ion battery cathode active material, which comprises a niobium pentoxide composite material; wherein the niobium pentoxide composite material comprises a niobium pentoxide composite material containing dopant ions and/or a coating layer. The niobium pentoxide composite material has excellent potassium ion transmission channels, can realize the rapid intercalation and de-intercalation of potassium ions, has stable crystal structure, adopts the reaction mechanism of intercalation and pseudocapacitance, can prepare the potassium ion battery with long cycle life, high specific capacity and low cost, can solve the problem of price rise caused by insufficient lithium resources, and can also avoid the problems of expansion and pulverization of the alloy type cathode of the potassium ion battery, slow dynamics of the intercalation type carbon material and the like. The energy storage device can be widely applied to electric tools, electronic equipment, electric vehicles or energy storage equipment.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products available by commercial purchase.
It should be noted that:
in the present invention, all the embodiments and preferred methods mentioned herein can be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, all the technical features mentioned herein and preferred features may be combined with each other to form a new technical solution, if not specifically stated.
In the present invention, the percentage (%) or parts means the weight percentage or parts by weight with respect to the composition, if not otherwise specified.
In the present invention, the components referred to or the preferred components thereof may be combined with each other to form a novel embodiment, if not specifically stated.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "55-70" indicates that all real numbers between "55-70" have been listed herein, and "55-70" is simply a shorthand representation of the combination of these numbers.
The "ranges" disclosed herein may have one or more lower limits and one or more upper limits, respectively, in the form of lower limits and upper limits.
In the present invention, unless otherwise specified, the individual reactions or operation steps may be performed sequentially or may be performed in sequence. Preferably, the reaction processes herein are carried out sequentially.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can be used in the present invention.
According to a first aspect of the present invention, there is provided a potassium ion battery negative active material comprising a niobium pentoxide composite material;
wherein the niobium pentoxide composite material comprises a niobium pentoxide composite material containing dopant ions and/or a cladding layer.
The invention provides a potassium ion battery cathode active material, which comprises a niobium pentoxide composite material; the niobium pentoxide composite material has an excellent potassium ion transmission channel, can realize the rapid intercalation and de-intercalation of potassium ions, has a stable crystal structure, adopts a reaction mechanism of intercalation and pseudocapacitance, has long cycle life, high specific capacity and low cost of the prepared potassium ion battery, can solve the problem of price rise caused by insufficient lithium resources, and can also avoid the problems of expansion and pulverization of an alloy type cathode of the potassium ion battery, slow dynamics of an intercalation type carbon material and the like. The energy-saving device can be widely applied to electric tools, electronic equipment, electric vehicles or energy storage equipment.
"doped ion-and/or clad-containing niobium pentoxide composite" refers to doped ion-containing niobium pentoxide composite, clad-containing niobium pentoxide composite, doped ion-and clad-containing niobium pentoxide composite.
The "niobium pentoxide composite material containing a coating layer" means that the surface of niobium pentoxide is coated with a coating layer, and the "niobium pentoxide composite material containing a dopant ion and a coating layer" means that the surface of niobium pentoxide composite material containing a dopant ion is coated with a coating layer. The material of the coating layer can be carbon material or metal oxide; optionally, the carbon material includes elemental carbon including, but not limited to, graphite, expanded graphite, graphene, mesocarbon microbeads graphite, acetylene black, glassy carbon, carbon-carbon composites, activated carbon, hard carbon, carbon black, carbon nanotubes, carbon nanofibers, or mesoporous carbon, and/or carbon-containing compounds including, but not limited to, citric acid, glucose, sucrose, starch, polyoxyethylene, polyethylene glycol, glycerol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl propyl cellulose, polyvinyl alcohol, polypropylene, phenolic resin, or epoxy resin; optionally, the metal oxide comprises titanium dioxide, manganese dioxide or ferric oxide.
The doped ions in the niobium pentoxide composite material containing doped ions can be metal elements or non-metal elements; for example, K, Na, Li, Mg, Zn, Ca, N, S or P may be mentioned.
The crystal form of niobium pentoxide is not particularly limited, and can be a crystal form of niobium pentoxide well known to those skilled in the art; for example, it may be an orthorhombic phase, a hexagonal phase or a monoclinic phase.
The morphology of niobium pentoxide is not limited, and may be a one-dimensional nanostructure, such as nanofiber or nanobelt, or a two-dimensional structure, such as nanosheet.
The source of niobium pentoxide is not particularly limited in the present invention, and niobium pentoxide known to those skilled in the art can be used; if it is commercially available, it can be prepared by itself by a method known to those skilled in the art.
It should be noted that the source and preparation method of the niobium pentoxide composite material containing the doped ions and/or the coating layer are not particularly limited in the present invention, and the niobium pentoxide composite material containing the doped ions and/or the coating layer, which is well known to those skilled in the art, can be used; if it is commercially available, it can be prepared by itself by a method known to those skilled in the art.
As a further preferred technical solution, the dopant ion includes K; in the preferred embodiment, the niobium pentoxide negative electrode doped with K can enlarge the interlayer spacing of niobium pentoxide to a certain extent, improve the specific capacity, and the K element contained in the negative electrode can timely supplement the K consumed by forming an SEI film in the electrolyte+。
As a further preferable technical scheme, the mass ratio of the doping ions K to the niobium element is 1: 3-1: 7.
In a more preferable embodiment, the mass ratio of the dopant ion K to the niobium element is 1: 5. In the preferred embodiment, the K doping amount is such that the cell performance is superior, and too much K doping amount is such that K is added+The diffusion channel is blocked, the doping amount is too small to enlarge the distance between niobium pentoxide layers, and the capacity is not obviously improved.
As a further preferable technical solution, the material of the coating layer is preferably graphene; in the preferred embodiment, the graphene has good conductivity, and the problem of poor conductivity of niobium pentoxide can be solved.
In a more preferable embodiment, the material of the coating layer is 5 to 20 wt%.
The mass fraction of the material of the coating layer means the percentage content of the mass of the coating layer in the total mass of the niobium pentoxide composite material.
In a more preferred embodiment, the mass fraction of the material of the coating layer is 10 wt%. In the preferred embodiment, the active material specific weight is reduced and the volume energy density is reduced due to excessive graphene, and the whole material surface cannot be sufficiently coated due to insufficient graphene, so that the conductivity is not remarkably improved.
In a more preferred embodiment, the niobium pentoxide composite material is a niobium pentoxide composite material containing a coating layer.
In a more preferred embodiment, the coating layer is a niobium pentoxide composite material of a carbon material.
According to a second aspect of the present invention, there is provided a potassium ion battery negative electrode material comprising the above potassium ion battery negative electrode active material, a conductive agent and a binder.
The potassium ion battery cathode material comprises a niobium pentoxide composite material, the niobium pentoxide composite material has an excellent potassium ion transmission channel, rapid embedding and de-embedding of potassium ions can be realized, the crystal structure is stable, and phase change does not occur in the embedding and de-embedding process of the potassium ions.
According to a third aspect of the present invention, there is provided a potassium-ion battery anode comprising the above potassium-ion battery anode active material.
The invention provides a potassium ion battery cathode which comprises a niobium pentoxide composite material, wherein the niobium pentoxide composite material has an excellent potassium ion transmission channel, can realize the rapid embedding and de-embedding of potassium ions, has a stable crystal structure, does not generate phase change in the embedding and de-embedding processes of the potassium ions, has a reaction mechanism of an intercalation mechanism and a pseudo-capacitance mechanism, and has the characteristics of long cycle life, high specific capacity and low cost.
The method for preparing the negative electrode material by using the negative electrode active material is well known to those skilled in the art, and the method for preparing the negative electrode material by using the negative electrode active material is not particularly limited; for example, a niobium pentoxide composite material, a conductive agent and a binder are mixed and then coated on the surface of a current collector to obtain the potassium ion battery negative electrode active material.
According to a fourth aspect of the present invention, there is provided a method for preparing the above potassium ion battery negative electrode, comprising the steps of:
dissolving a potassium ion battery negative electrode active material, a conductive agent and a binder in a solvent to prepare slurry, and then coating the slurry on the surface of a negative electrode current collector to obtain the potassium ion battery negative electrode.
The conductive agent includes, but is not limited to, carbon black.
Binders include, but are not limited to, polyvinylidene fluoride.
Solvents include, but are not limited to, NMP (N-methylpyrrolidone) or water.
The cathode material is made into slurry, and a cathode material layer is formed after coating, so that the cathode is obtained, and the preparation method is simple.
According to a fifth aspect of the present invention, there is provided a potassium ion battery comprising the above potassium ion battery negative electrode or the potassium ion battery negative electrode prepared by the above preparation method, a positive electrode, a separator, and an electrolyte.
The invention provides a potassium ion battery, wherein a negative electrode of the potassium ion battery comprises the potassium ion battery negative electrode active material, a niobium pentoxide composite material is used as a negative electrode active substance, the niobium pentoxide composite material has an excellent potassium ion transmission channel, can realize the rapid embedding and de-embedding of potassium ions, has a stable crystal structure, does not generate phase change in the embedding and de-embedding processes of the potassium ions, and has a reaction mechanism of an intercalation mechanism and a pseudocapacitance mechanism, so that the potassium ion battery has the advantages of long cycle life, high specific capacity and low cost.
The positive electrode is not particularly limited, and may be formed using a layered metal oxide, a polyanion compound or a prussian blue analog, which are available in the art, including but not limited to K0.67Fe0.5Mn0.5O2、 FePO4、K0.5MnO2Or K2Fe2(CN)6Is optionally K0.67Fe0.5Mn0.5O2。
The separator is not particularly limited, and may be a porous polymer film, an inorganic porous film, or an organic-inorganic composite separator as known in the art, including but not limited to one of a porous ceramic film, a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, or glass fiber.
It should be understood that the electrolyte includes a potassium salt and a non-aqueous solvent.
The potassium salt is not particularly limited, and any potassium salt known in the art may be used, and includes, but is not limited to, at least one of potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalate borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methanesulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonimide, and potassium trifluoromethanesulfonate, and potassium hexafluorophosphate may be used.
The non-aqueous solvent is not particularly limited, and may be one existing in the art, and includes, but is not limited to, at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, methylethyl carbonate, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, ethyl propionate, methyl propionate, ethyl acetate, γ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, or diethyl sulfite or crown ether, and may be selected from ethylene carbonate, propylene carbonate, diethyl carbonate, or crown ether, A mixed solvent of dimethyl carbonate and ethyl methyl carbonate.
In a more preferred embodiment, the separator is made of glass fiber.
As a further preferable technical scheme, the concentration of the potassium salt in the electrolyte is 0.1-8mol/L, preferably 0.5-1 mol/L;
in a further preferable technical scheme, in the mixed solvent of ethylene carbonate, propylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the volume ratio of the ethylene carbonate, the propylene carbonate, the dimethyl carbonate and the ethyl methyl carbonate is 2:2:3: 3.
The structural shape of the potassium ion battery is not limited, and the potassium ion battery can be a button battery, a columnar battery or a soft package battery.
According to a sixth aspect of the present invention, there is provided the use of the above potassium ion battery in an electric tool, an electronic device, an electric vehicle, or an energy storage device.
Power tools may use potassium ion batteries as the moving parts of the driving power source, including but not limited to electric drills and the like; the electronic device is a potassium ion battery as an operating power supply to perform various functions, including but not limited to a mobile phone, a notebook computer, a desktop computer or an electronic watch; the electric vehicle is an electric vehicle which runs by using a potassium ion battery as a driving power supply, and comprises but is not limited to an electric vehicle and the like; the large-scale energy storage equipment uses potassium ion batteries as energy storage units, and includes but is not limited to substations or wind generating sets and the like.
The same effect can be obtained by using the potassium ion battery of the invention for electric tools, electronic equipment, electric vehicles or large-scale energy storage equipment.
The technical solution of the present invention will be further described with reference to examples and comparative examples.
Example 1
1. Potassium ion battery negative active material
A potassium ion battery negative active material comprises a niobium pentoxide composite material; the niobium pentoxide composite material is a niobium pentoxide composite material containing a coating layer.
Wherein the coating layer is made of carbon material, and the mass fraction of the carbon material is 10 wt%. The preparation of the niobium pentoxide composite material comprises the following steps: adding 8mmol of niobium pentachloride and 1.47mmol of citric acid into 100mL of deionized water, quickly stirring uniformly, adding 30g of sodium chloride, stirring for 30min, freezing with liquid nitrogen, freeze-drying for 24h, keeping the temperature in a tube furnace at 700 ℃ under argon atmosphere for 1h, cooling naturally, repeatedly washing with deionized water and absolute ethyl alcohol to remove a template, and drying at 60 ℃ in vacuum overnight to obtain the niobium pentoxide composite material Nb2O5@C。
2. Potassium ion battery cathode
The potassium ion battery cathode comprises a niobium pentoxide composite material Nb2O5@C。
Preparing a potassium ion battery cathode: 0.8g of niobium pentoxide composite material Nb2O5Adding @ C powder, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into an agate mortar, fully grinding, and then dripping a proper amount of N-methylpyrrolidone to mix into uniform slurry; the slurry was then uniformly coated on the surface of the nickel foam (i.e., the negative current collector) and vacuum dried. Cutting the dried electrode slice into a wafer with the diameter of 12mm, and compacting to obtain the potassium ion battery negative electrode active material.
3. Potassium ion battery
The potassium ion battery has a negative electrode made of the potassium ion battery negative active material and a positive electrode made of K0.67Fe0.5Mn0.5O2Electric powerThe hydrolysate is KPF6The content of the solution is 0.8M, the solvent is EC: PC: DMC: EMC 2:2:3:3 (v/v/v), and the diaphragm is glass fiber. And assembling the battery at room temperature, tightly stacking the prepared cathode, the diaphragm and the battery anode in sequence, adding an electrolyte to completely soak the diaphragm, and then packaging the stacked part into a battery shell to finish the battery assembly.
Examples 2 to 16
Examples 2 to 16 are different from example 1 in that the negative electrode material active material is different, specifically, as shown in table 1.
Table 1 negative electrode material active material
Figure BDA0001908810510000131
Figure BDA0001908810510000141
In Table 1, @ C denotes carbon-coated @ TiO2Represents TiO2Cladding, Nb2O5@MnO2@TiO2Indicates that MnO is first performed2Coating, then TiO2And (4) coating.
Examples 19 to 21
Examples 19-21 differ from example 1 in that the separator is different, as shown in table 2.
TABLE 2 separator
Diaphragm
Example 1 Glass fiber
Example 19 Polyethylene (PE)
Example 20 Polypropylene (PP)
Example 21 Double layer PP/PE
Examples 22 to 24
Examples 22 to 24 are different from example 1 in that the positive electrode is different, as shown in table 2.
TABLE 3 Positive electrode
Positive electrode
Example 1 K0.67Fe0.5Mn0.5O2
Example 22 FePO4
Example 23 K0.5MnO2
Example 24 K2FeFe(CN)6
Comparative example 1
Comparative example 1 differs from example 1 in that Sn foil is used as the negative electrode active material.
Comparative example 2
Comparative example 2 differs from example 1 in that a natural graphite was used as the negative electrode active material.
Comparative example 3
Comparative example 3 differs from example 1 in that bismuth metal is used as the negative electrode active material.
Test example 1
The potassium ion batteries of examples 1 to 24 and comparative examples 1 to 3 were subjected to electrochemical performance test with an electrolyte of 0.8M KPF6EC PC DMC EMC 2:2:3:3(v/v/v/v), and the diaphragm is glass fiber. And assembling the battery in a room temperature environment, tightly stacking the prepared cathode, the diaphragm and the potassium sheet in turn, adding electrolyte to completely soak the diaphragm, and packaging the stacked part into a battery shell to finish battery assembly. The battery test comprises specific capacity and cycle number, and the specific test method comprises the following steps:
specific capacity: cyclic charge and discharge are performed on a CT2001A battery cycle test system, the standard capacity of an electrode is tested by charging and discharging at a current density of 50mA/g, the voltage interval is 1-4V, the specific capacity C ═ It/m (I current, t time, m active material mass) of a material, the energy density E ═ CV (C specific capacity, V voltage) of the material, and the charging and discharging process is as follows: standing for 600s, and then performing charge-discharge circulation, wherein the circulation step comprises the following steps: constant current charging-constant current discharging.
Cycle number: the cycle performance of the battery is tested by charging and discharging at a current density of 50mA/g on a battery cycle test system, the cycle performance of the battery is represented by the number of cycles when the discharge depth (DOD) of the battery is reduced to 80%, the battery is kept still for 600s and then subjected to charge and discharge cycles, and the cycle steps are the same as the cycle charge and discharge. The results obtained are shown in table 4.
TABLE 4 electrochemical Properties
Figure BDA0001908810510000151
As can be seen from Table 4, the potassium ion battery with the negative electrode made of the niobium pentoxide composite material has high specific capacity and long cycle life. As shown in Table 4, the niobium pentoxide composite material has a stable crystal structure, has an excellent potassium ion transmission channel, and can realize rapid insertion and extraction of potassium ions. And the potassium ion batteries prepared by the negative electrode materials of the comparative examples 1 to 3 have lower specific capacity.
Comparison of examples 17-20 with example 1 shows that the positive electrode has an effect on the cell performance, using K from example 10.67Fe0.5Mn0.5O2The positive pole effect is better. It can be seen from the comparison of examples 20-23 with example 1 that the separator has an effect on the battery performance, and the effect is better with the glass fiber separator of example 1.
It should be understood that the contents not described in detail in the description of the above preparation method are common parameters that can be easily conceived by those skilled in the art, and thus, detailed description thereof may be omitted.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A potassium ion battery negative electrode active material is characterized by comprising a niobium pentoxide composite material;
wherein the niobium pentoxide composite material comprises a niobium pentoxide composite material containing dopant ions and/or a cladding layer;
the doping ions comprise at least one of K, Na, Li, Mg, Zn, Ca, N, S or P;
the material of the coating layer comprises at least one of a carbon material and a metal oxide;
the carbon material comprises a simple substance carbon and/or a carbon-containing compound;
the carbon simple substance comprises at least one of graphite, expanded graphite, graphene, mesocarbon microbeads, acetylene black, glassy carbon, a carbon-carbon composite material, activated carbon, hard carbon, carbon black, carbon nanotubes, carbon nanofibers or mesoporous carbon;
the carbon-containing compound comprises at least one of citric acid, glucose, sucrose, starch, polyoxyethylene, polyethylene glycol, glycerol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl propyl cellulose, polyvinyl alcohol, polypropylene, phenolic resin or epoxy resin;
the metal oxide comprises at least one of titanium dioxide, manganese dioxide and ferric oxide.
2. The potassium ion battery anode active material according to claim 1, wherein the dopant ion is K;
the mass ratio of the doping ions to the niobium element is 1: 3-1: 7;
the crystal form of niobium pentoxide includes at least one of an orthorhombic phase, a hexagonal phase, and a monoclinic phase.
3. The potassium-ion battery negative active material according to claim 1,
the coating layer is made of graphene;
the mass fraction of the material of the coating layer is 5 wt% -20 wt%.
4. The negative active material of a potassium ion battery according to any one of claims 1 to 3, wherein the niobium pentoxide composite material is a niobium pentoxide composite material containing a coating layer.
5. A potassium-ion battery negative electrode material, characterized by comprising the potassium-ion battery negative electrode active material according to any one of claims 1 to 4, a conductive agent, and a binder.
6. A potassium-ion battery negative electrode comprising a negative electrode current collector and the potassium-ion battery negative electrode material according to claim 5.
7. The method for preparing the negative electrode of the potassium ion battery as claimed in claim 6, characterized by comprising the steps of:
dissolving a potassium ion battery negative electrode active material, a conductive agent and a binder in a solvent to prepare slurry, and then coating the slurry on the surface of a negative electrode current collector to obtain the potassium ion battery negative electrode.
8. A potassium ion battery, which is characterized by comprising the potassium ion battery negative electrode of claim 6 or the potassium ion battery negative electrode prepared by the preparation method of claim 7, a positive electrode, a separator and an electrolyte.
9. The potassium-ion battery of claim 8, wherein the positive electrode comprises a layered metal oxide, a polyanionic compound, or a prussian blue analog;
the diaphragm comprises a porous polymer film, an inorganic porous film or an organic-inorganic composite diaphragm;
the electrolyte comprises a potassium salt and a non-aqueous solvent;
the concentration of potassium salt in the electrolyte is 0.1-8 mol/L;
the potassium salt comprises at least one of potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalato borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methylsulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonimide or potassium trifluoromethanesulfonate;
the non-aqueous solvent comprises at least one of ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, ethyl propionate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite or diethyl sulfite or crown ether;
in the mixed solvent of the ethylene carbonate, the propylene carbonate, the dimethyl carbonate and the ethyl methyl carbonate, the volume ratio of the ethylene carbonate, the propylene carbonate, the dimethyl carbonate and the ethyl methyl carbonate is 2:2:3: 3.
10. Use of the potassium ion battery of claim 8 or 9 in a power tool, an electronic device, an electric vehicle, or an energy storage device.
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